Biomass Group, Nanjing Agricultural University, PO Box 68, 40 Dianjiangtai Road, Nanjing 210031

Sustainable production of aromatic-rich biofuel via catalytic co-pyrolysis of lignin and waste polyoxymethylene over commercial Al₂O₃ catalyst

Recently, under the guidance of Associate Professor Lu-jiang Xu, master student Mr. Ge-liang Xie published an article on the preparation of high aromatic biofuels by lignin and waste polyoxymethylene (POM) catalytic co-pyrolysis in the journal Journal of Analytical and Applied Pyrolysis.

Co-valorization of biomass and multiple solid wastes is essential to environment protection and energy security. Herein, aromatic-rich biofuel was produced from lignin and waste polyoxymethylene (POM) via catalytic co-pyrolysis process. Commercial and cheap γ-Al₂O₃ catalyst exhibited good catalytic performance. Series characterizations and bench-top pyrolysis experiments were conducted to illustrate the synergism between raw materials and the mechanism of aromatics formation. The TG analysis and thermodynamics calculation revealed that a remarkably positive synergistic effect existed between lignin and POM, could reduce the activation energies, and make the reaction more conducive in terms of thermodynamics. Meanwhile, the yields of biochar and bio-oil increased considerably Additionally, the operating conditions affected the product distributions significantly. The suitable mixing ratio of lignin to POM was around equal (5:5) with the bio-oil yield increased by 25% to 28.3% and aromatic hydrocarbons selectivity increased to >95%. Moreover, POM, the precursor for alkylating reagents and hydrogen donors, could promote the deoxygenation reactions of phenolic intermediates and result into aromatic hydrocarbons. The acid sites of γ-Al₂O₃ promoted series secondary cracking reactions (alkylation, deoxygenation), and thus improve bio-oil quality. Finally, the stability test showed that commercial γ-Al₂O₃ catalyst was slightly deactivated after 4 cycles because of coke deposits and acid sites loss.

Related results were published in Journal of Analysis and Applied Pyrolysis:

GL Xie, GQ Zhu, T Lv, YF Kang, YH Chen, Z Fang, LJ Xu*, Sustainable production of aromatic-rich biofuel via catalytic co-pyrolysis of lignin and waste polyoxymethylene over commercial Al₂O₃ catalyst, Journal of Analytical and Applied Pyrolysis, 174, 106147, https://authors.elsevier.com/c/1hiQybaW~3r4b (2023).

Using lignin and waste acetal (POM) as raw materials and commercial γ-Al₂O₃ as catalyst, aromatic-rich biofuels were prepared by catalytic co-pyrolysis process. The suitable mixing ratio of lignin and polyoxymethylene was about 5∶5, the yield of bio-oil increased by 25% to 28.3%, and the selectivity of aromatic hydrocarbons increased to >95%.以木质素和废聚甲醛（POM）为原料，商业γ-Al₂O₃作为催化剂，采用催化共热解工艺制备了富含芳烃的生物燃料。在木质素与聚甲醛的适宜混合比例下（5∶5），生物油收率提高了25%至28.3%，芳烃选择性提高至>95%。

通过商业Al₂O₃催化剂催化木质素和废聚甲醛的共热解可持续生产富含芳烃的生物燃料

近日，在徐禄江副教授的指导下，硕士生谢葛亮先生在《分析与应用热解杂志》（IF 6.0）上发表了一篇关于木质素与废聚甲醛催化共热解制备高芳烃生物燃料的研究性论文。

生物质和多种固体废物的联合定价对环境保护和能源安全至关重要。以木质素和废聚甲醛（POM）为原料，采用催化共热解工艺制备了富含芳烃的生物燃料。市售廉价的γ-Al₂O₃催化剂具有良好的催化性能。通过系列表征和台架热解实验，阐明了原料之间的协同作用和芳烃的形成机理。TG分析和热力学计算表明，木质素与聚甲醛之间存在显著的正协同作用，可以降低活化能，使反应在热力学上更有利于进行。同时，生物炭和生物油的产率显著提高，操作条件对产物分布有显著影响。木质素与聚甲醛的适宜混合比例约为5∶5，生物油收率提高了25%至28.3%，芳烃选择性提高至>95%。此外，POM作为烷基化试剂和氢供体的前体，可以促进酚类中间体的脱氧反应，生成芳烃。γ-Al₂O₃的酸性位点促进了一系列的二次裂化反应（烷基化、脱氧），从而提高了生物油的质量。最后，稳定性测试表明，商业γ-Al₂O₃催化剂在4次循环后由于焦炭沉积和酸位损失而轻微失活。

结果发表在Journal of Analysis and Applied Pyrolysis:

GL Xie, GQ Zhu, T Lv, YF Kang, YH Chen, Z Fang, LJ Xu*, Sustainable production of aromatic-rich biofuel via catalytic co-pyrolysis of lignin and waste polyoxymethylene over commercial Al₂O₃ catalyst, Journal of Analytical and Applied Pyrolysis, 174, 106147, https://authors.elsevier.com/c/1hiQybaW~3r4b (2023).

Two-stage process production of microbial lipid by co-fermentation of glucose and N-acetylglucosamine from food wastes with Cryptococcus curvatus

Recently, master student Mr. Jia-xuan Zhang supervised by Prof. Zhen Fang published a research article in Bioresource Technology about Two-stage fermentation of food waste (rice and shrimp shells hydrolysates) by Cryptococcus curvatus for lipids.

Microbial lipids were produced through a two-stage process with Cryptococcus curvatus by co-fermenting rice and shrimp shells hydrolysates. The main components of the lipid sample were long-chain fatty acids with carbon chain lengths of 16 and 18, which were similar to those of typical vegetable oils. And the lipid sample showed high potential for biodiesel production. In the shake flask fermentation, co-utilization of N-acetylglucosamine (GlcNAc) and glucose resulted in improved cell mass and lipid production. The highest cell concentration of 17.60 g/L was achieved in the first-stage, and the highest lipid yield was 0.233 g/g in the second- stage. Scaling up to a 5-L bioreactor increased lipid content to 60.07 % with 0.233 g/g yield. When Cryptococcus curvatus was cultured in the blends of rice hydrolysates and shrimp shells hydrolysate, lipid content and yield were 52.25 % and 0.204 g/g. Co-fermentation of rice hydrolysates and chitin hydrolysate is an effective means for recycling food wastes for lipids.

Related results were published in Bioresource Technology:

JX Zhang, XL Liu, L Wang, Zhen Fang*, Two-stage process production of microbial lipid by co-fermentation of glucose and N-acetylglucosamine from food wastes with Cryptococcus curvatus, Bioresource Technology, 387, 129685, https://doi.org/10,1016/j.biortech.2023.129685 (2023).

Two-stage process production of microbial lipid by co-fermentation with rice and shrimp shells hydrolysates from food wastes was carried out. After 36 h of the first-stage fermentation, 12.51 g/L of glucose and 9.91 g/L of GlcNAc were consumed simultaneously with 12.18 g/L cell mass produced. Transferring 6 g/L of yeast cells to the second-stage fermentation medium, cell mass of 19.44 g/L, lipid content of 52.25 %, and lipid yield of 0.204 g/g were obtained, respectively. (以食品废弃物中的大米水解物和虾壳的水解物为原料，采用两阶段共发酵工艺生产微生物油脂。在第一阶段发酵36 h后，12.51 g/L 葡萄糖和9.91 g/L N -乙酰氨基葡萄糖被消耗，细胞产量为12.18 g/L。然后将6g/L的酵母细胞转移到第二阶段发酵培养基中。分别获得19.44g/L的细胞质量、52.25%的脂质含量和0.204g/g的脂质产率。

Cryptococcus curvatus共发酵食品废弃物中葡萄糖和N –乙酰氨基葡萄糖两阶段工艺生产微生物脂质

最近，硕士生张家璇（男）在方真教授的指导下，在国际学术期刊Bioresource Technology （Q1, IF 11.4）发表一篇关于两阶段共发酵来自食品废弃物的葡萄糖和N-乙酰氨基葡萄糖生产微生物油脂的研究性论文。

以Cryptococcus curvatus 为研究对象，通过共发酵大米水解物和虾壳的水解物，利用两阶段工艺制备微生物脂质。脂质样品的主要成分是碳链长度为16和18的长链脂肪酸，与典型的植物油相似。脂质样品显示出生产生物柴油的较高潜力。在摇瓶发酵中，N-乙酰氨基葡萄糖（GlcNAc）和葡萄糖的共同利用提高了细胞质量和脂质产量。在第一阶段达到17.60g/L的最高细胞浓度，在第二阶段达到0.233g/g的最高脂质产率。扩大至5-L生物反应器发酵，可将脂质含量提高到60.07%，产量为0.233g/g。Cryptococcus curvatus在大米水解物和虾壳水解物的混合物中培养时，脂质含量和产量分别为52.25%和0.204g/g。大米水解物和甲壳素水解物的联合发酵是回收食品垃圾的有效途径。

结果发表在Bioresource Technology：

JX Zhang, XL Liu, L Wang, Zhen Fang*, Two-stage process production of microbial lipid by co-fermentation of glucose and N-acetylglucosamine from food wastes with Cryptococcus curvatus, Bioresource Technology, 387, 129685, https://doi.org/10,1016/j.biortech.2023.129685 (2023).

A green process for biodiesel and hydrogen coproduction from waste oils with a magnetic metal-organic framework derived material

Recently, Dr. Wen-jie Cong (female) supervised by Prof. Zhen Fang published a research article in Biomass & Bioenergy about biodiesel and hydrogen coproduction from waste oils with a solid base derived from magnetic metal-organic framework.

Magnetic self-assembly metal-organic frameworks (MOFs) were constructed for the co-production of biodiesel and hydrogen from waste oils. The highly active MOF nanoparticles were synthesized and catalyzed crude glycerol for 126.8% hydrogen yield in subcritical water (350 ℃, 5 min). By coupling alkali with MOF-derived carriers, continuous process of fast production of biodiesel (with microwave heating at 90 ℃ in 15 min, 15:1 methanol/oil molar ratio and 9 wt.% catalyst dosage) and hydrogen (350 ℃, 5 min) were achieved with yield of 95.3% biodiesel from waste oil (AV was 3.95 mg KOH) and 102.6% H2 from crude glycerol by-product, respectively. The nanoparticles were magnetically separated for 5 cycles with 95% biodiesel yield and increased hydrogen yield by 50% after deactivated. Characterization techniques showed active sites of MOF-derived nanoparticles were well dispersed with surface area increased by 3.9 times for highly efficient production of biodiesel and hydrogen. It revealed that MOF materials can be designed to make active catalysts and carriers for loading catalytic sites for biomass conversions to targeted biofuels.

A self-assembled nano Ni-MOF was synthesized as magnetic carrier and catalyst support for biodiesel and hydrothermal hydrogen production from waste oils. (以自组装纳米Ni-MOF作为磁性载体制备催化剂，以废弃油脂为原料联合生产生物柴油和氢气）

Related results were accepted in Biomass & Bioenergy:

WJ Cong, J Yang, JG Zhang, Zhen Fang^*, ZD Miao. A green process for biodiesel and hydrogen coproduction from waste oils with a magnetic metal-organic framework derived material. Biomass & Bioenergy. 175 (2023) 106871. https://doi.org/10.1016/j.biombioe.2023.106871.

磁性金属有机骨架衍生材料用于废油联产生物柴油和氢气的绿色工艺

最近，丛文杰博士（女）在方老师的指导下，在国际学术期刊Biomass & Bioenergy（IF5.77，Q1）发表金属有机框架衍生固体碱联合制备生物柴油和氢气的研究性论文。

本研究通过制备自组装磁性纳米金属有机骨架 (Ni-MOF)，构建了以废弃油为原料联合制备生物柴油和氢气的绿色工艺。在亚临界水（350 ℃，5 min）条件下，该高活性Ni-MOF纳米颗粒催化粗甘油水热制氢，氢气产率高达126.8%。以该Ni-MOF为载体制备磁性固体碱，实现高酸值废弃油（酸值3.95 mg KOH）制备生物柴油，产率为95.3%（90 ℃、15 min、甲醇/油摩尔比15:1、催化剂用量为9 wt.%），该磁性固体碱经磁性分离后重复使用5次，生物柴油产率为95%；失活后的磁性固体碱用于水热气化副产物粗甘油制备氢气，产率为102.6%（350 ℃，5 min），氢气产率提高了50%。研究结果表明该Ni-MOF纳米颗粒活性位点分散性好，比表面积增加了3.9倍，可高效联产生物柴油和氢气。该MOF材料可以设计成多功能磁性载体和高性能催化剂，用于负载高活性催化位点实现生物质快速转化为生物燃料。

详情可见：

WJ Cong, J Yang, JG Zhang, Zhen Fang^*, ZD Miao. A green process for biodiesel and hydrogen coproduction from waste oils with a magnetic metal-organic framework derived material. Biomass & Bioenergy. 175 (2023) 106871. https://doi.org/10.1016/j.biombioe.2023.106871.

Efficient lipid synthesis of Chlorella pyrenoidosa promoted under heavy metals from electric arc furnace slag

Recently, Dr Yi-Tong Wang (female, Associate Professor, College of Metallurgy and Energy, North China University of Science and Technology) and Prof. Zhen Fang published an article in Journal of Cleaner Production (IF: 11.072, Q1) about using efficient lipid synthesis of Chlorella pyrenoidosa microalgae promoted under heavy metals from electric arc furnace slag.

Electric arc furnace slag is highly productive and rich in elements, which can be used as a nutrient source for microalgae. The study investigated the regulation of growth and lipid synthesis of Chlorella pyrenoidosa in electric arc furnace slag leaching solution, and citric acid electric arc furnace slag co-leaching solution, to achieve lipid production while treating metallurgical solid waste. The results showed that the highest biomass and lipid contents were 0.23 g/L and 45.89 wt%, respectively, when BG11 was added to the electric arc furnace slag leaching solution. The highest biomass and lipid contents were 0.25 g/L and 33.37 wt%, respectively, for the addition of citric acid electric arc furnace slag leaching solution at BG11. Various metal ions in the electric arc furnace slag leaching solution increased the biomass lipid content by modulating acetyl-CoA carboxylase, malic enzyme, and phosphoenolpyruvate carboxylase activities. This study helps to solve the problem of the high cost of microalgae culture and metallurgical solid waste treatment while generating lipids and provides a new green pathway for the commercialization of microalgae.

Related results were accepted in Journal of Cleaner Production:

Q Yu, TJ Liu, YN Zeng, YT Wang*, JG Li*, LL Kang, R Ji, FP Wang, XM Wang, B Liu, S Cai, Zhen Fang*. Efficient lipid synthesis of Chlorella pyrenoidosa promoted under heavy metals from electric arc furnace slag. Journal of Cleaner Production, 2023, 414, 137648. https://doi.org/10.1016/j.jclepro.2023.137648

High lipid content (45.89 wt%) was obtained by adding EAFS leaching solution into BG11. High biomass content (0.44 g/L) was achieved by citric acid assisting EAFS leaching. 在BG11中加入EAFS浸出液，获得了较高的脂质含量(45.89 wt%)。柠檬酸辅助EAFS浸出可获得较高的生物质含量(0.44 g/L)。

电炉渣重金属胁迫促进Chlorella pyrenoidosa微藻高效合成油脂

最近，青年女科学家王一同博士（华北理工大学冶金与能源学院副教授）和方真教授在国际学术期刊Journal of Cleaner Production（IF: 11.072，Q1）发表题为“电炉渣重金属胁迫促进Chlorella pyrenoidosa高效合成脂质”的研究性论文。

电炉渣产量高，元素丰富，可作为微藻的营养来源。研究了Chlorella pyrenoidosa在电炉渣浸出液和柠檬酸电炉渣共浸出液中的生长和脂质合成的调节机制，实现冶金固体废物资源化同时获得高附加值脂质。结果表明，当在BG11添加电炉渣浸出液中时，生物量和脂质的最高含量分别为0.23g/L和45.89wt%。在BG11添加柠檬酸电炉渣联合浸出液时，生物量和脂质含量分别为0.25g/L和33.37wt%。电炉渣浸出液中的各种金属离子通过调节乙酰辅酶A羧化酶、苹果酸酶和磷酸烯醇丙酮酸羧化酶的活性来增加脂质含量。本研究有助于解决微藻培养和冶金固废处理成本高的问题，为微藻商业化提供新思路。详情可见：

Q Yu, TJ Liu, YN Zeng, YT Wang*, JG Li*, LL Kang, R Ji, FP Wang, XM Wang, B Liu, S Cai, Zhen Fang*. Efficient lipid synthesis of Chlorella pyrenoidosa promoted under heavy metals from electric arc furnace slag. Journal of Cleaner Production, 2023, 414, 137648. https://doi.org/10.1016/j.jclepro.2023.137648

Miss Xiao-le Liu and Mr. Jian Yang successfully defended their Doctoral and Master theses

On May 26, 2023, Miss Xiao-le Liu and Mr. Jian Yang, supervised by Prof. Zhen Fang, successfully defended their theses at C302 Yuxian Building, Pukou Campus of Nanjing Agricultural University. The defending committee was composed of Prof. Mao-hua Xiao (Chair) from Nanjing Agricultural University, Profs Wei Zhuang and Jun Zhou from Nanjing Tech University as well as Profs Chang-ying Ji, Wei-min Ding and Chun-xia He from Nanjing Agricultural University (NJAU).

Miss Liu and Mr. Yang presented their research results for doctoral and master theses, the committee members raised relevant questions. Based on the replies and theses reviewed, the panels agreed that Miss Liu and Mr. Yang had successfully completed their research and course requirements in agricultural bio-environment and energy engineering. Miss Liu studied the production of microbial lipid from wheat straw with dissertation entitled “Study on mechanochemical pretreatment of wheat straw and enzymatic hydrolysate for microbial lipid production”. She significantly improved the enzymatic hydrolysis efficiency of wheat straw pretreated by solid particle-assisted ball milling pretreatment, and realized the efficient production of lipid from the enzymatic hydrolysis of pretreated wheat straw. Mr. Yang studied biodiesel production of waste cooking oil by bifunctional magnetic catalysts with his thesis entitled “Microwave Assisted Production of Biodiesel from Waste Cooking Oil by Bifunctional SrO-ZnO/MOF Catalyst”. Miss Liu published 2 academic papers and Mr. Yang published 1 academic papers. Both of them had all been awarded the title of “Outstanding Graduate of NJAU”. Mr. Yang won President Scholarship of NJAU.

After the juries voted by secret ballot, the panels agreed to confer Doctor of Philosophy in Engineering to Miss Xiao-Le Liu, and Master of Engineering degree to Mr. Yang Jian, subjected to the approval by the Academic Degrees Committees of the college and university.

Congratulations to Miss Liu and Mr. Yang!

Papers published:

XL Liu, Zhen Fang*, XF Tian*, ZD Miao, Impact of Alkalic Salt Coupled Ball Milling Pretreatment of Wheat Straw on Improving Enzymatic Hydrolysis and Energy Efficiency, Fuel, 340 (2023), 127336. https://doi.org/10.1016/j.fuel.2022.127336.

XL Liu, CY Dong, SY Leu, Zhen Fang*, ZD Miao, Efficient Saccharification of Wheat Straw Pretreated by Solid Particle-Assisted Ball Milling with Waste Washing Liquor Recycling, Bioresource Technology, 347 (2022), 126721. https://doi.org/10.1016/j.biortech.2022.126721.

Jian Yang, Wen-Jie Cong, Zongyuan Zhu**, Zheng-diao Miao, Yi-Tong Wang***, Michael Nelles, Zhen Fang*. Microwave-assisted one-step production of biodiesel from waste cooking oil by magnetic bifunctional SrO–ZnO/MOF catalyst. Journal of Cleaner Production, 395 (2023) 136182. https://doi.org/10.1016/j.jclepro.2023.136182.

刘小乐和杨剑同志顺利通过博士和硕士论文答辩

2023年5月26日上午，南京农业大学生物能源组2019级博士研究生刘小乐（女）和硕士生杨剑（导师方真教授）毕业答辩会在南京农业大学浦口校区育贤楼C302举行。南京农业大学的肖茂华教授担任答辩评审委员会主席，南京工业大学的庄伟教授和周俊教授，南京农业大学的丁为民，姬长英教授和何春霞教授共五位专家担任评审委员。

答辩会上，刘小乐同学和杨剑同学对其在校期间的学术论文进行汇报，同时答辩委员会主席和各位评委提出了相关问题。根据刘小乐同学和杨剑同学的问题回答以及学位论文的评阅，评委会经过评审决议，一致认为刘小乐同学和杨剑同学顺利完成了农业生物环境与能源方面的研究和学习要求。刘小乐同学在毕业论文《机械化学法预处理小麦秸秆及其酶解液发酵产微生物油脂的研究》中研究了球磨和化学颗粒结合预处理小麦秸秆，实现了小麦秸秆的结构解聚，有效提高了小麦秸秆在较低酶载量和较短时间内的酶水解效率，并将水解获得的可发酵性碳源用于发酵产微生物油脂，实现了农作物秸秆到微生物油脂的资源化利用。杨剑同学在毕业论文《双功能SrO-ZnO/MOF催化剂微波辅助餐厨废油制备生物柴油》中研究了利用双功能磁性催化剂催化废油脂制备生物柴油，实现了在较温和条件下一步法催化高酸值废弃油制备生物柴油。刘小乐同学以第一作者身份共发表学术论文2篇，杨剑同学以第一作者发表学术论文1篇，两人均获得2023南京农业大学优秀毕业生称号。杨剑同学获得南京农业大学校长奖学金。

经评委会无记名投票表决，一致同意刘小乐同学通过博士学位论文答辩，建议授予工学博士学位；杨剑同学通过硕士学位论文答辩，建议授予杨剑工学硕士学位。

 祝贺刘小乐和杨剑同学！

发表的论文：

XL Liu, Zhen Fang*, XF Tian*, ZD Miao, Impact of Alkalic Salt Coupled Ball Milling Pretreatment of Wheat Straw on Improving Enzymatic Hydrolysis and Energy Efficiency, Fuel, 340 (2023), 127336. https://doi.org/10.1016/j.fuel.2022.127336.

XL Liu, CY Dong, SY Leu, Zhen Fang*, ZD Miao, Efficient Saccharification of Wheat Straw Pretreated by Solid Particle-Assisted Ball Milling with Waste Washing Liquor Recycling, Bioresource Technology, 347 (2022), 126721. https://doi.org/10.1016/j.biortech.2022.126721.

Jian Yang, Wen-Jie Cong, Zongyuan Zhu**, Zheng-diao Miao, Yi-Tong Wang***, Michael Nelles, Zhen Fang*. Microwave-assisted one-step production of biodiesel from waste cooking oil by magnetic bifunctional SrO–ZnO/MOF catalyst. Journal of Cleaner Production, 395 (2023) 136182. https://doi.org/10.1016/j.jclepro.2023.136182.